硝酸铁和磷酸共沉淀法制备电池级磷酸铁工艺研究

doi:10.19964/j.issn.1006-4990.2022-0548

Abstract

Abstract:

By using ferric nitrate and phosphoric acid as raw materials，the co-precipitation method was used to prepare the battery grade ferric phosphate.The effects of reaction temperature，reactant concentration，feeding proportion and reaction time on the yield and particle size of ferric phosphate were studied，and the optimal process conditions were obtained through orthogonal optimization：the solution concentration of Fe（NO₃）₃ was 1.1 mol/L，the feed ratio of phosphoric acid to ferric nitrate was 1.1，the reaction temperature was 90 ℃，and the reaction time was 8 h.The prepared iron phosphate was characterized by scanning electron microscopy（SEM），laser particle size analyzer，X-ray diffractometer（XRD） and TG-DTA.The analysis results showed that the obtained ferrophosphate dihydrate was monoclinic crystal with high purity and secondary particle size D₅₀ of 2.41 μm，which met the requirements of battery grade ferrophosphate.The performance of LiFePO₄/C prepared by the precursor system of iron phosphate was good.The initial discharge specific capacity of the battery composed of iron phosphate as cathode materials were 143.9，136.8 and 131.4 mA·h/g at 0.05C，0.1C and 1C，respectively.

Key words: ferric nitrate, ferric phosphate, co-precipitation method, lithium iron phosphate, orthogonal experiment

CLC Number:

TQ138.1

WANG Zihan, LI Jun, CHEN Ming, ZHOU Qingyu. Study on preparation of battery grade ferric phosphate by co-precipitation of ferric nitrate and phosphoric acid[J]. Inorganic Chemicals Industry, 2023, 55(7): 51-57.

Figures/Tables 15

Fig.1

Fig.2

Fig.3

Fig.4

Table 1

Table 2

Table 3

Fig.5

Fig.6

Fig.7

Fig.8

Fig.9

Fig.10

Fig.11

Table 4

References 15

1	张克杰，陈鹏，谢旺旺，等.磷酸铁锂优缺点及改性研究进展［J］.无机盐工业，2018，50（6）：13-17.
	ZHANG Kejie， CHEN Peng， XIE Wangwang，et al.Progress in modification of lithium iron phosphate and its advantages and disadvantages［J］.Inorganic Chemicals Industry，2018，50（6）：13-17.
2	梁广川.锂离子电池用磷酸铁锂正极材料［M］.北京：科学出版社，2013：288-292.
3	张婷，林森，于建国.磷酸铁锂正极材料的制备及性能强化研究进展［J］.无机盐工业，2021，53（6）：31-40.
	ZHANG Ting， LIN Sen， YU Jianguo.Research progress in synthesis and performance enhancement of LiFePO₄ cathode materials［J］.Inorganic Chemicals Industry，2021，53（6）：31-40.
4	刘贡钢，叶红齐，刘辉，等.前驱体磷酸铁的制备及其对磷酸
	铁锂电化学性能的影响［J］.应用化工，2013，42（2）：225- 228.
	LIU Gonggang， YE Hongqi， LIU Hui，et al.Preparation of precursor FePO₄ and its effects on electrochemical properties of LiFePO₄ ［J］.Applied Chemical Industry，2013，42（2）：225-228.
5	袁静楠.不同晶型磷酸铁的制备及与磷酸亚铁锂间的相互转换关系［D］.郑州：郑州大学，2012.
	YUAN Jingnan.Preparation of different crystal forms of iron phosphate and their conversion relationship with lithium ferrous phosphate［D］.Zhengzhou：Zhengzhou University，2012.
6	姚停，徐婷，宋磊，等.磷酸铁形貌对磷酸铁锂倍率性能的影响［J］.电池，2020，50（1）：54-57.
	YAO Ting， XU Ting， SONG Lei，et al.Effects of morphology of ferric phosphate on rate capability of lithium iron phosphate［J］.Battery Bimonthly，2020，50（1）：54-57.
7	吴康，李军，陈明.乙醇-水体系3D纳/微米球形磷酸铁的制备与表征［J］.无机盐工业，2020，52（6）：41-45.
	WU Kang， LI Jun， CHEN Ming.Synthesis and characterization of 3D nano/micro spherical iron phosphate in ethanol-water system［J］.Inorganic Chemicals Industry，2020，52（6）：41-45.
8	马志鸣，肖仁贵，廖霞，等.片层纳米结构磷酸铁制备及对磷酸铁锂电性能的影响［J］.材料导报，2018，32（19）：3325-3331.
	MA Zhiming， XIAO Rengui， LIAO Xia，et al.Preparation of the lameller nanostructure iron phosphate and its effect on the electrochemical performance of lithium iron phosphate［J］.Materials Review，2018，32（19）：3325-3331.
9	赵曼.水热法以磷铁制备电池级磷酸铁及改性研究［D］.贵阳：贵州大学，2017.
	ZHAO Man.Preparation of battery-grade iron phosphate from ferrophosphorus by hydrothermal method and its modification［D］.Guiyang：Guizhou University，2017.
10	严鹏，谢刚，张春明，等.非晶态磷酸铁的沉淀反应机理及性能［J］.电池，2015，45（5）：241-243.
	YAN Peng， XIE Gang， ZHANG Chunming，et al.Precipitation reaction mechanism and performance of amorphous ferric phosphate［J］.Battery Bimonthly，2015，45（5）：241-243.
11	张震，蒲薇华，任建国，等.控制结晶法制备球形磷酸铁的团聚尺寸模型［J］.化学工程，2011，39（8）：20-24.
	ZHANG Zhen， PU Weihua， REN Jianguo，et al.Agglomeration-size model of ferric phosphate spherical particle prepared by controlled crystallization［J］.Chemical Engineering（China），2011，39（8）：20-24.
12	李永佳，魏润宏，鲁劲华，等.电池级磷酸铁的制备及性能［J］.化工进展，2021，40（4）：2227-2233.
	LI Yongjia， WEI Runhong， LU Jinhua，et al.Preparation and performance of FePO₄ precursor for LiFePO₄ ［J］.Chemical Industry and Engineering Progress，2021，40（4）：2227-2233.
13	郑典模，潘鹤政，伍丽萍，等.超细磷酸铁的制备及其电化学性能研究［J］.电源技术，2015，39（1）：58-61.
	ZHENG Dianmo， PAN Hezheng， WU Liping，et al.Study on preparation and electrochemical of ultrafine FePO₄ ［J］.Chinese Journal of Power Sources，2015，39（1）：58-61.
14	李文升，樊勇利，童书辉，等.高振密球形FePO₄·xH₂O的合成研究［J］.电源技术，2013，37（6）：950-952.
	LI Wensheng， FAN Yongli， TONG Shuhui，et al.Synthesis research on iron phosphate with spherical structure and high tap density［J］.Chinese Journal of Power Sources，2013，37（6）：950-952.
15	ZHANG Tongbao， XIN Dawei， LU Yangcheng，et al.Direct precipitation for a continuous synthesis of nanoiron phosphate with high purity［J］.Industrial & Engineering Chemistry Research，2014，53（16）：6723-6729.

水平	因素
水平	A 反应温度/℃	B 反应物浓度/ （mol·L^-1）	C 投料比	D 反应时间/h
1	80	0.2	1.1	8
2	85	0.5	1.3	9
3	90	0.8	1.5	10
4	95	1.1	1.7	11

实验	实验因素					二次粒径/μm
实验	A	B	C	D	空白实验	二次粒径/μm
1	1	1	1	1	1	4.23
2	1	2	2	2	2	12.2
3	1	3	3	3	3	9.12
4	1	4	4	4	4	2.52
5	2	1	2	4	3	5.95
6	2	2	1	3	4	6.98
7	2	3	4	2	1	9.23
8	2	4	3	1	2	3.86
9	3	1	3	2	4	2.88
10	3	2	4	1	3	2.58
11	3	3	1	4	2	2.87
12	3	4	2	3	1	3.01
13	4	1	4	3	2	3.83
14	4	2	3	4	1	9.06
15	4	3	2	1	4	10.7
16	4	4	1	2	3	2.56
K₁	28.07	16.89	16.64	21.37	25.53
K₂	26.02	30.82	31.86	26.87	22.76
K₃	11.34	31.92	24.92	22.94	20.21
K₄	26.15	11.95	18.16	20.40	23.08
k₁	7.02	4.22	4.16	5.34	6.38
k₂	6.51	7.71	7.97	6.72	5.69
k₃	2.84	7.98	6.23	5.74	5.05
k₄	6.54	2.99	4.54	5.10	5.77
R	4.18	4.99	3.81	1.62	1.33

方差来源	偏差平方和	自由度	方差	F值	F_α	显著性
A	41.67	3	13.89	3.90	F_0.005（1，9）=13.61	*
B	75.03	3	25.01	7.02	F_0.05（1，9）=5.12	**
C	36.50	3	12.17	3.42	F_0.10（1，9）=3.36	*
D	6.09	3	2.03	0.57
误差	10.69	3	3.56
总和	169.98	15

[1]	ZHAO Runze, QIAN A′niu. Research progress of lithium recovery for spent lithium-ion batteries and preparation in battery-grade lithium carbonate [J]. Inorganic Chemicals Industry, 2024, 56(12): 70-78.
[2]	LI Ping, LI Jun, CHEN Ming. Study on process of recovery of Fe（Ⅲ） from spent lithium extractant and preparation of battery grade iron phosphate [J]. Inorganic Chemicals Industry, 2024, 56(10): 28-37.
[3]	PAN Xiaoxiao, ZHUANG Shuxin, SUN Yuqing, SUN Gaoxing, REN Yan, JIANG Shengyu. Research progress of modified-LiFePO₄ as cathode materials for lithium ion batteries [J]. Inorganic Chemicals Industry, 2023, 55(6): 18-26.
[4]	CHEN Yujue, ZHANG Liangjun, KUANG Huan, JIANG Manwen, XIAO Li. Study on roasting and recovery process of waste lithium iron phosphate powder with sodium bisulfate [J]. Inorganic Chemicals Industry, 2023, 55(3): 113-117.
[5]	CHEN Zhangxu, FU Minglian, ZHU Danchen, ZHENG Bingyun. Preparation of carbon/graphite carbon nitride composites and their methylene blue removal performance [J]. Inorganic Chemicals Industry, 2023, 55(3): 134-139.
[6]	GONG Jiazhu,ZHOU Guimin,WU Ninglan,WANG Weilin,QIAO Guangqin. Challenges and innovative development opportunities of carbon peak and carbon neutralization faced by inorganic salt industry [J]. Inorganic Chemicals Industry, 2022, 54(4): 46-54.
[7]	YANG Wenyu,LIN Zhiya,FU Hong,YAN Wenyue,LIN Jianping,GUAN Guiqing. Study on surface potential of lithium iron phosphate based on kelvin probe technology [J]. Inorganic Chemicals Industry, 2022, 54(11): 65-70.
[8]	Zhang Ting,Lin Sen,Yu Jianguo. Research progress in synthesis and performance enhancement of LiFePO₄ cathode materials [J]. Inorganic Chemicals Industry, 2021, 53(6): 31-40.
[9]	HE Yanjun,ZHENG Hanxiao,LÜ Li,TANG Shengwei. Carbothermal reduction process of low-grade mixed phosphate ore [J]. Inorganic Chemicals Industry, 2021, 53(11): 95-99.
[10]	Liu Peiwen,Dong Peng,Meng Qi,Yang Xuan,Zhou Siyuan. Research development of solid phase regeneration of cathode material of spent lithium iron phosphate batteries [J]. Inorganic Chemicals Industry, 2020, 52(9): 6-8.
[11]	Guo Ju,Jia Shuangzhu. Study on the one-step hydrothermal synthesis of LiFePO₄ and its properties [J]. Inorganic Chemicals Industry, 2020, 52(6): 36-40.
[12]	Wang Jiatai,Zhao Duan,Ma Lianhua,Zhang Caihong. Research progress of LiFePO₄ cathode materials for Li-ion battery [J]. Inorganic Chemicals Industry, 2020, 52(4): 18-22.
[13]	Li Jieen,He Binbin,Yang Xiushan,Xu Dehua,Zhang Zhiye. Study on phosphorus extraction and impurity reduction technology for pretreatment of middle-low grade phosphate ore [J]. Inorganic Chemicals Industry, 2020, 52(4): 33-36.
[14]	Su Wei,Zhang Linfeng,Lü Qingyang,Xia Yuyan,Yuan Hua. Synthesis of diphenyl carbonate by oxidative carbonylation over palladium loaded MnO_x-based bimetallic oxide catalysis [J]. Inorganic Chemicals Industry, 2019, 51(9): 91-96.
[15]	Chen Lei,Zhao Longtao,Chen Zhenyu,Li Guang. Preparation of spherical lithium iron phosphate material and its 18650 battery test [J]. Inorganic Chemicals Industry, 2019, 51(8): 25-28.

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Study on preparation of battery grade ferric phosphate by co-precipitation of ferric nitrate and phosphoric acid

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 15

References 15

Related Articles 15

Metrics

Comments

Recommended 0